Silver halide crystals formed during in situ treatment of silver stearate crystals with various halidizing agents are observed by scanning and transmission electron microscopy to form on the lateral edges of the silver carboxylate crystals. The location of the silver halide phase on the crystal edge is dictated by the anisotropic structure of the silver stearate crystal lattice, specifically, the layered structure in which silver ion layers are separated by long‐chain hydrocarbon groups. The formation of AgBr on the lateral faces of these crystals is proposed to be typical not only of the formation of silver halide on silver stearate but also for all silver carboxylates of the general formula [AgCnH2n‐1O2]2 when the crystals of these silver carboxylates have anisotropic, layered structures. The silver bromide/silver carboxylate heterojunction in an in situ system has been clearly observed by transmission electron microscopy. The heterojunction is comprised of a distorted silver carboxylate lattice, which accommodates the misalignment between the AgBr and [Ag(O2CR)]2 crystal lattices. The nature of heterojunction between the AgBr and the silver carboxylate when the AgBr is prepared separately from the preparation of the silver carboxylate differs from the in situ heterojunction. In this case, a layered compound, proposed to have a Ag1‐xNaxSt composition, forms between the AgBr and the silver stearate which is a unique feature of this interface. The differences in the structure of interfaces formed between the silver halide and the silver fatty acid complex result in different silver particle morphologies during thermal development of exposed photothermographic films. The developed silver is generally filamentary when the photothermographic material contains silver halide prepared by the in situ exchange reaction between silver carboxylate and a brominating agent. If the photothermographic material is prepared from previously synthesized silver halide crystals, the preformed AgBr route, the developed silver generally crystallizes as dendritic crystals. Microsc. Res. Tech. 42:152–172, 1998. © 1998 Wiley‐Liss, Inc.
